WO2008093916A1 - Composition de plastifiant contenant des dérivés de cyclodextrine, composition de pvc flexible à migration du plastifiant est supprimée, et procédé de production de ces compositions - Google Patents
Composition de plastifiant contenant des dérivés de cyclodextrine, composition de pvc flexible à migration du plastifiant est supprimée, et procédé de production de ces compositions Download PDFInfo
- Publication number
- WO2008093916A1 WO2008093916A1 PCT/KR2007/002585 KR2007002585W WO2008093916A1 WO 2008093916 A1 WO2008093916 A1 WO 2008093916A1 KR 2007002585 W KR2007002585 W KR 2007002585W WO 2008093916 A1 WO2008093916 A1 WO 2008093916A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- plasticizer
- phthalate
- migration
- chemistry
- suppression
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/203—Solid polymers with solid and/or liquid additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
- C08L2666/26—Natural polymers, natural resins or derivatives thereof according to C08L1/00 - C08L5/00, C08L89/00, C08L93/00, C08L97/00 or C08L99/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/16—Cyclodextrin; Derivatives thereof
Definitions
- the present invention relates to a method for manufacturing a flexible PVC, which mixes PVC and a low molecular weight liquid plasticizer to manufacture the flexible PVC, and in particular, to a plasticizer composition which is mixed with a low molecular weight liquid plasticizer to form a complex, thereby suppressing plasticizer migration when used as a plasticizer, a manufacturing method of a flexible PVC composition with suppression of the migration of plasticizer containing the same, and the flexible PVC composition with suppression of the migration of plasticizer, manufactured thereby.
- Poly(vinyl chloride) is a typical all-purpose resin that has wide applications, for example pipes, materials for packaging foods, fiber for textiles, interior decorations, blood storage containers or products for infants such as nursing bottles or toys.
- PVC has a limitation in molecular mobility due to its unique hierarchy structure and microcrystallite serving as physical crosslinks, and thus exhibits hard characteristics, and by this reason, PVC should be provided with flexibility through a plasticization process for use of flexible characteristics, for example a film for packaging foods.
- a flexible PVC is manufactured such that PVC resin is mixed with a low molecular weight liquid plasticizer to form a plastisol, which is heated so that the PVC is dissolved in the low molecular weight liquid plasticizer and then cooled.
- Known low molecular weight liquid plasticizers include phthalate plasticizers, phosphate plasticizers, trimellitate plasticizers and aliphatic diester plasticizers, and may further include epoxy plasticizers and anti-chlorine plasticizer.
- the low molecular weight liquid plasticizer considerably improves the molecular mobility of PVC, to provide the PVC with flexibility.
- the low molecular weight liquid plasticizer may be useful in providing the PVC with flexibility, but has inherent physical properties of a low molecular weight liquid material, for example volatilization into the air or outward transfer through contact with liquid or solid materials. It has been reported that, when a plasticizer migrating from PVC enters the bodies of animals or plants, the plasticizer may disrupt a normal activity of the endocrine system directly involved with vital activities or cause an abnormal reaction of the endocrine system, thereby resulting in a fatal harm to the bodies of animals or plants.
- a cyclodextrin is a cyclic compound composed of repeating glucose units and can be represented by the following Chemistry Figure 2.
- n the number of repeating glucose units is an integer of 6 to 26, preferably
- the cyclodextrin has a hydrophilic outer part surrounded by hydroxyl functional groups, and a hydrophobic inner cavity.
- the cyclodextrin may form a complex with a plasticizer having such a size as to enter the inner cavity, i.e. a low molecular weight liquid plasticizer.
- the low molecular weight liquid plasticizer may be drawn and fixed into the inner cavity by hydrophobic interaction or through hydrogen bonds.
- the cyclodextrin mixed with PVC and the low molecular weight liquid plasticizer has a poor dispersibility, and thus forms aggregates, thereby considerably reducing its capability of suppressing plasticizer migration and deteriorating physical properties of the resultant flexible PVC.
- the above-mentioned papers suggested to disperse PVC, DOP and cyclodextrin in a dimethylacetamide (DMAc) solvent and cast the resultant mixture to manufacture a flexible PVC with suppressed plasticizer migration.
- DMAc dimethylacetamide
- the present invention is designed to solve the problems of the prior art, and therefore it is an object of the present invention to provide a manufacturing method of a flexible PVC composition with suppression of plasticizer migration.
- the inventive method allows mass-production of flexible PVC compositions capable of suppressing plasticizer migration in a simple and efficient manner with no need of a solvent while supporting a dramatic reduction in plasticizer leaks and less deterioration of physical properties in the resultant flexible PVC.
- a manufacturing method of a flexible PVC composition with suppressed plasticizer migration includes (Sl) preparing a cyclodextrin derivative represented by the following Chemistry Figure 3; (S2) mixing the cyclodextrin derivative, PVC and a low molecular weight liquid plasticizer to form a plastisol; and (S3) heating the plastisol into liquid and cooling the plastisol:
- each R having 1 to 20 carbon atoms, is a functional group independent of one another, represented by the following Chemistry Figure 4 and has a degree of substitution of 5 to 100%, and n is an integer of 6 to 26, and
- a, b, c, d, e, f and g each respectively is an integer of at least 0 with a+b+c+d+e+f+g being at least 1 , and wherein the linking order among said constituent units of a, b, c, d, e, f and g can vary at random, and R is benzene, benzene derivatives, naphthalene, or naphthalene derivatives.
- the manufacturing method according to the present invention supports the mass- production of flexible PVC with suppressed plasticizer migration in a simple and economical manner with no need of a solvent.
- the inventive method is capable of considerably reducing the amount of migrating plasticizers without deteriorating the physical properties of the resultant flexible PVC.
- the cy- clodextrin derivatives have the content of 2 to 20 mol based on 100 mol content of the low molecular weight liquid plasticizer.
- the low molecular weight liquid plasticizer may include any one or mixtures of at least one selected from the group consisting of a phthalate plasticizer such as dimethyl phthalate (DMP), dibutyl phthalate (DBP), di-isobutyl phthalate (DIBP), dihexyl phthalate (DHP), dioctyl phthalate (DOP), diisooctyl phthalate (DIOP), dinonyl phthalate (DNP), di-isodecyl phthalate (DIDP) and benzyl butyl phthalate (BBP), an aliphatic diester plasticizer such as dioctyl adipate (DOA), diisooctyl adipate (DIOA) and diisodecyl adipate (DIDA), a trimellitate plasticizer such as triisooctyl
- a phthalate plasticizer such as dimethyl phthalate (DMP), dibutyl
- FIG. 1 is a view schematically illustrating the structure of alpha-cyclodextrin derivatives as an embodiment of cyclodextrin derivatives used in the present invention.
- FIG. 2 is a view schematically illustrating the structure of cyclodextrin derivatives which form a complex by drawing DOP into an inner cavity in the plasticizer composition of the present invention.
- FIG. 3 is a view schematically illustrating the structure of a flexible PVC composition with suppressed plasticizer migration, in which PVC, a low molecular weight liquid plasticizer and a cyclodextrin derivative are uniformly mixed according to the present invention.
- FIG. 1 is a view schematically illustrating the structure of alpha-cyclodextrin derivatives as an embodiment of cyclodextrin derivatives used in the present invention.
- FIG. 2 is a view schematically illustrating the structure of cyclodextrin derivatives which form a complex by drawing DOP into an inner cavity in the plasticizer composition of the present invention.
- FIG. 4 is a surface photograph of a sample (PVC-O) of comparison example 1 containing no cyclodextrin derivatives.
- FIG. 5 is a surface photograph of a sample (PVC-3) of comparison example 3 containing a predetermined amount of cyclodextrin derivatives.
- FIG. 6 is a surface photograph of a sample manufactured by dispersing a pure beta- cyclodextrin in DMAc solution according to the prior art.
- FIG. 7 is a calibration curve of absorbance of standard solutions manufactured for evaluation of migration concentration of a phthalate plasticizer.
- FIG. 8 is a graph illustrating DOP migration test results of flexible PVC samples with suppression of plasticizer migration according to the present invention.
- FIG. 9 is a stress-strain curve graph of flexible PVC samples with suppression of plasticizer migration according to the present invention.
- R is a functional group, which replaces the hydrogen of a hydroxyl functional group.
- Each R is independently a functional group having 1 to 20 carbon atoms, represented by the following Chemistry Figure 4, and R has a degree of substitution of 5 to 100%, and n is an integer of 6 to 26 (preferably 6 to 8).
- R has a degree of substitution of 5 to 100 %, preferably
- a, b, c, d, e, f and g each is an integer of at least 0 with a+b+c+d+e+f+g being at least 1 , and the linking order among the constituent units of a, b, c, d, e, f and g can vary at random.
- R is benzene, benzene derivatives, naphthalene, or naphthalene derivatives.
- a functional group represented by the above Chemistry Figure 4 may be any one selected from the group consisting of benzoyl, naphthyl, naphthoyl, anthracene and their derivatives, however the present invention is not limited in this regard.
- hydroxyl hydrogens may be substituted by another functional group in such a range represented by R of Chemistry Figure 4 to the above-mentioned degree, and preferably the hydroxyl hydrogens are substituted by silane functional groups having 1 to 60 carbon atoms, represented by the following Chemistry Figure 8.
- R , R and R each is independently a functional group having 1 to 20 carbon atoms, represented by the Chemistry Figure 4.
- the silane functional group represented by the Chemistry Figure 5 may include trimethyl silane, butyldimethyl silane, methoxy silane, ethoxy silane or methacryloxypropyl trimethoxy silane, however the present invention is not limited in this regard.
- Such cyclodextrin derivatives may be manufactured by reacting the cyclodextrin represented by the Chemistry Figure 2 with a compound represented by the following Chemistry Figure 6.
- R is the same as R of the Chemistry Figure 3
- X is a functional group that can react with the hydroxyl functional group of the cyclodextrin represented by the Chemistry Figure 2, and for example, may include a halogen atom, a hydroxyl functional group or an alkoxy functional group.
- R is the same as R of the Chemistry Figure 3
- X is a functional group that can react with the hydroxyl functional group of the cyclodextrin represented by the Chemistry Figure 2, and for example, may include a halogen atom, a hydroxyl functional group or an alkoxy functional group.
- the cyclodextrin derivatives represented by Chemistry Figure 3 in which the hydrogen functional group is substituted by certain compounds, have good dispersibility when the cyclodextrin derivatives are mixed with PVC and the low molecular weight liquid plasticizer. Therefore, it is possible to form a plastisol having the cyclodextrin derivatives uniformly dispersed therein without a solution such as DMAc used in the prior art. As a result, a flexible PVC with suppression of plasticizer migration may be mass- produced in a simple and economical manner.
- the cyclodextrin derivatives have the content of 2 to 20 mol based on
- the low molecular weight liquid plasticizer may be any material capable of forming a complex through the inner cavity of the cyclodextrin derivatives.
- the low molecular weight liquid plasticizer may be a typical low molecular weight liquid plasticizer used to make PVC flexible, for example any one or mixtures of at least one selected from the group consisting of phthalate plasticizers such as dimethyl phthalate (DMP), dibutyl phthalate (DBP), di-isobutyl phthalate (DIBP), dihexyl phthalate (DHP), dioctyl phthalate (DOP), diisooctyl phthalate (DIOP), dinonyl phthalate (DNP), di- isodecyl phthalate (DIDP) and benzyl butyl phthalate (BBP), an aliphatic diester plasticizer such as dioctyl adip
- DMP dimethyl phthalate
- DBP dibutyl phthalate
- a mixing ratio of PVC and the low molecular weight liquid plasticizer may be changed according to the desired ductility, which is apparent to an ordinary person in the art. For example, 10 to 80 parts by weight of the plasticizer is used based on 100 parts by weight of the PVC.
- the plastisol may be formed by simultaneously mixing the cyclodextrin derivatives, and PVC and the low molecular weight liquid plasticizer, or first mixing the cyclodextrin derivatives and the low molecular weight liquid plasticizer to form a plasticizer composition and then mixing the plasticizer composition with PVC.
- the plasticizer composition containing the cyclodextrin derivatives and the low molecular weight liquid plasticizer is first formed according to the present invention, and may be used instead of a typical plasticizer of PVC.
- FIG. 1 is a view schematically illustrating the structure of alpha-cyclodextrin derivatives as an embodiment of cyclodextrin derivatives used in the present invention.
- each alpha-cyclodextrin derivative has an inner cavity.
- Such cyclodextrin derivatives draw the low molecular weight liquid plasticizer, for example DOP into the inner cavity to form a complex, thereby preventing migration of the plasticizer (See FIG. 2). That is, as shown in FIG. 3, the flexible PVC composition of the present invention in which PVC, the low molecular weight liquid plasticizer and cyclodextrin derivative are uniformly dispersed, supports an efficient formation of a complex between the cyclodextrin derivatives and DOP. This improves the suppressing efficiency of plasticizer migration without deteriorating of the physical properties of the flexible PVC.
- Na- ⁇ -CD 2,3,6-tri- O -naphthoyl- ⁇ -cyclodextrin
- Chemistry Figure 7 was synthesized according to a method disclosed in the Journal of American Chemical Society 1992, Vol. 114, P. 6427-6436 "Multi- chromophoric cylodextrins. 1. Synthesis of o-naphthoyl- ⁇ -cyclodextrins and investigation of excimer formation and energy hopping".
- beta-cyclodextrin used in the reaction was purchased from Tokyo Kasei. 11.35 g (0.01 mol) of beta-cyclodextrin was dissolved in 150 ml of pyridine. Next, an excess of naphthoyl chloride was slowly dropped, agitated at 70 0 C for about seven days, and separately extracted using ethyl acetate. The extracted organic layer was washed with 1 M of hydrochloric acid solution, and then dehydrated using Na SO water. Then, the pyridine solution was removed under reduced pressure to obtain a precipitate.
- the resultant Na- ⁇ -CD product was performed elementary analysis for carbon, hydrogen and oxygen atoms to calculate a weight ratio of each of the elements, and on the basis of the calculation, it was defined how much hydrogen of the terminal hydroxyl functional group of the beta-cyclodextrin was substituted, and according to the results, it was found that 19 hydroxyl functional groups corresponding to about 90.5 % among a total of 21 hydroxyl functional groups of the beta-cyclodextrin were substituted in the reaction with naphthoyl chloride.
- This embodiment shows a manufacturing method of the flexible PVC composition with suppression of plasticizer migration using the cyclodextrin derivatives manufactured in synthetic example 1.
- the PVC used was a commercial one (LG Chem. Ltd., LP 170), and the plasticizer used was a typical low molecular weight liquid plasticizer, for example dioctyl phthalate (hereinafter referred to as DOP).
- DOP dioctyl phthalate
- the second plasticizer used, an epoxidized soybean oil was SDB CIZER-E03 made by Shin Dong Bang Corporation, and the heat stabilizer used was MT-800 made by Songwon Industrial Co., Ltd.
- the resultant plastisol was matured in a vacuum oven for about 2 weeks, and a predetermined amount of the plastisol was put into a frame and heated in a processing oven at 18O 0 C for about 5 to 10 minutes, and then was placed at a room temperature to manufacture flexible PVC samples with suppression of plasticizer migration.
- the manufactured samples were numbered according to the wt% of the content of cyclodextrin derivatives based on a total content of plastisol.
- plastisols with cyclodextrin derivative contents of 0, 2.5, 3.7 and 5.8 wt% were designated as PVC-O, PVC-I, PVC-2 and PVC-3, respectively.
- FIG. 4 is a surface photograph of the sample (PVC-O) of comparison example 1 containing no cyclodextrin derivatives
- FIG. 5 is a surface photograph of the sample (PVC-3) of comparison example 3 containing a predetermined amount of cyclodextrin derivatives
- FIG. 6 is a surface photograph of a sample manufactured by dispersing a pure beta-cyclodextrin in DMAc solution according to the prior art.
- the manufactured flexible PVC samples were tested for plasticizer migration through the below-mentioned process.
- the migration test was carried out in conformity with conditions based on a method of ISO (International Standard Organization) 3826 "Plastics collapsible containers for human blood and blood components".
- the DOP standard solution was manufactured to have DOP content of 1, 2, 5, 10 or
- the DOP migration solution was prepared by suitably mixing ethyl alcohol and water so that a density of the ethyl alcohol/water mixed solution was 0.9373 to 0.9378 g/ml.
- the used ethyl alcohol had a purity of 95.1 to 96.6 % (v/v) and a density of 0.8050 to 0.8123 g/ml.
- Ig of DOP was added to the ethyl alcohol so that the mixed solution had a volume of 100 ml. 10 ml of the mixed solution was diluted with the migration solution so that the diluted solution had a volume of 100 ml.
- the manufactured flexible PVC samples were put into 100 g of the migration solution and sealed tightly, and maintained at an ambient temperature of 37+1 0 C. And, the absorbance of the migration solutions was measured at the wavelength of 272 nm using the UV- vis. spectrophotometer at regular time intervals, the measured absorbance was applied to the calibration curve to calculate the concentration of DOP migrated from the samples, and the result is shown in the following Table 2 and FIG. 8. The unit of the Table 2 is mg/lOOml.
- the manufacturing method of flexible PVC with suppression of plasticizer migration uses cyclodextrin derivatives.
- These derivatives are cyclodextrins substituted by certain compounds that form a complex with the low molecular weight liquid plasticizer.
- the use of such cyclodextrin derivatives allows mass-producing the flexible PVC with suppression of plasticizer migration in simple and economical manner without using a solvent.
- the manufactured flexible PVC has the low molecular weight liquid plasticizer and the cyclodextrin derivatives uniformly dispersed therein, and the cyclodextrin derivatives form a complex with the low molecular weight liquid plasticizer, thereby improving a suppressing efficiency of plasticizer migration without deterioration of its mechanical property.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Medicinal Preparation (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
L'invention concerne une composition de plastifiant contenant des dérivés de cyclodextrine, une composition de PVC flexible dans laquelle la migration du plastifiant est inhibée, contenant cette composition de plastifiant, et un procédé de production de la composition de PVC. Le procédé de production comprend les étapes suivantes: (S1) préparation d'un dérivé de cyclodextrine dans lequel les hydrogènes de la cyclodextrine sont substitués par un composant déterminé; (S2) mélange du dérivé de cyclodextrine, du PVC et d'un plastifiant liquide à faible masse moléculaire pour former un plastisol; et (S3) chauffage du plastisol pour le liquéfier puis refroidissement du plastisol. Ce procédé de production comprend 'utilisation d e dérivés de cyclodextrine, les cyclodextrines étant modifiées par certains composés, et ces dérivés forment un complexe avec le plastifiant liquide à faible poids moléculaire pour bloquer la migration du plastifiant. Ce procédé permet par conséquent la production à grande échelle de PVC flexible exempt de migration de plastifiant, d'une manière simple et économique et sans utiliser de solvant.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2007-0010023 | 2007-01-31 | ||
KR1020070010023A KR100864991B1 (ko) | 2007-01-31 | 2007-01-31 | 사이클로덱스트린 유도체를 도입한 가소제 조성물, 이를포함하는 가소제 유출 저감형 연질 pvc 조성물 및 그제조방법 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2008093916A1 true WO2008093916A1 (fr) | 2008-08-07 |
Family
ID=39674206
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/KR2007/002585 WO2008093916A1 (fr) | 2007-01-31 | 2007-05-29 | Composition de plastifiant contenant des dérivés de cyclodextrine, composition de pvc flexible à migration du plastifiant est supprimée, et procédé de production de ces compositions |
Country Status (3)
Country | Link |
---|---|
US (1) | US20080200592A1 (fr) |
KR (1) | KR100864991B1 (fr) |
WO (1) | WO2008093916A1 (fr) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2007066839A1 (fr) * | 2005-12-07 | 2007-06-14 | Seoul National University Industry Foundation | Composition de plastifiant contenant des derives de cyclodextrine, composition de pvc souple sans migration de plastifiant contenant ladite composition, et procede de fabrication associe |
KR100718280B1 (ko) * | 2006-06-08 | 2007-05-16 | 재단법인서울대학교산학협력재단 | 사이클로덱스트린 유도체 입자를 도입한 가소제 유출저감형 폴리염화비닐 성형체 및 그 제조방법 |
WO2014100864A1 (fr) * | 2012-12-28 | 2014-07-03 | Braskem S.A. | Composition polymère et son utilisation, procédé de polymérisation et produit |
CN104072915A (zh) * | 2014-07-10 | 2014-10-01 | 上海新上化高分子材料有限公司 | 耐辐照灭菌医用聚氯乙烯材料及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5492947A (en) * | 1994-06-23 | 1996-02-20 | Aspen Research Corporation | Barrier material comprising a thermoplastic and a compatible cyclodextrin derivative |
US5696186A (en) * | 1995-03-21 | 1997-12-09 | Roquette Freres | Process for improving the mutual compatibility of polymers |
US5777003A (en) * | 1994-11-10 | 1998-07-07 | Wacker-Chemie Gmbh | Redispersible polymer powder composition comprising cyclodextrins or cyclodextrin derivitaves |
EP1291383A1 (fr) * | 2001-08-23 | 2003-03-12 | Cellresin Technologies, LLC | Récipient doté de propriétés de barrière aux substances organoleptiques améliorées |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100676942B1 (ko) * | 2005-12-07 | 2007-02-02 | 재단법인서울대학교산학협력재단 | 사이클로덱스트린 유도체를 도입한 가소제 조성물, 이를포함하는 가소제 유출 저감형 연질 pvc 조성물 및 그제조방법 |
-
2007
- 2007-01-31 KR KR1020070010023A patent/KR100864991B1/ko active IP Right Grant
- 2007-05-29 WO PCT/KR2007/002585 patent/WO2008093916A1/fr active Application Filing
-
2008
- 2008-01-29 US US12/011,837 patent/US20080200592A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5492947A (en) * | 1994-06-23 | 1996-02-20 | Aspen Research Corporation | Barrier material comprising a thermoplastic and a compatible cyclodextrin derivative |
US5777003A (en) * | 1994-11-10 | 1998-07-07 | Wacker-Chemie Gmbh | Redispersible polymer powder composition comprising cyclodextrins or cyclodextrin derivitaves |
US5696186A (en) * | 1995-03-21 | 1997-12-09 | Roquette Freres | Process for improving the mutual compatibility of polymers |
EP1291383A1 (fr) * | 2001-08-23 | 2003-03-12 | Cellresin Technologies, LLC | Récipient doté de propriétés de barrière aux substances organoleptiques améliorées |
Also Published As
Publication number | Publication date |
---|---|
KR100864991B1 (ko) | 2008-10-23 |
US20080200592A1 (en) | 2008-08-21 |
KR20080071754A (ko) | 2008-08-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5057277A (en) | Chemically sensitive, dimensionally-stable organosilicon material composition | |
US5194391A (en) | Chemically sensitive, dimensionally-stable organosilicon material composition and techniques | |
JP2984881B2 (ja) | プラスチツク材料の安定剤 | |
US2732357A (en) | Suspensions of polymeric chlorotri- | |
CN105622913B (zh) | 一种溶液法合成嵌段聚合物接枝纳米二氧化硅的方法 | |
DE202017007336U1 (de) | Biologisch abbaubare Polyesterzusammensetzung | |
WO2008093916A1 (fr) | Composition de plastifiant contenant des dérivés de cyclodextrine, composition de pvc flexible à migration du plastifiant est supprimée, et procédé de production de ces compositions | |
Bruna et al. | A novel polymer based on MtCu2+/cellulose acetate with antimicrobial activity | |
Yu et al. | Gelation/fusion behavior of PVC plastisol with a cyclodextrin derivative and an anti-migration plasticizer in flexible PVC | |
WO2017152772A1 (fr) | Composition de polyester biodégradable | |
US8008376B2 (en) | Plasticizer composition containing cyclodextrin derivatives, flexible PVC composition with suppression of the migration of plasticizer containing the same, and manufacturing method thereof | |
Chen et al. | Effect of storage condition on the physico-chemical properties of corn–wheat starch/zein edible bilayer films | |
US8008375B2 (en) | Poly(vinyl chloride) product containing cyclodextrin derivatives with suppression of the migration of plasticizer and manufacturing method thereof | |
Ramji et al. | Influence of NiO supported silica nanoparticles on mechanical, barrier, optical and antibacterial properties of polylactic acid (PLA) bio nanocomposite films for food packaging applications | |
US20070072988A1 (en) | Tricarboxylic acid ester plasticizers and methods of making | |
KR100676942B1 (ko) | 사이클로덱스트린 유도체를 도입한 가소제 조성물, 이를포함하는 가소제 유출 저감형 연질 pvc 조성물 및 그제조방법 | |
KR100953721B1 (ko) | 연질 pvc 조성물 | |
Chuayjuljit et al. | Effects of silica, poly (methyl methacrylate) and poly (methyl methacrylate)-grafted-silica nanoparticles on the physical properties of plasticized-poly (vinyl chloride) | |
JPWO2017141938A1 (ja) | セルロースアセテート組成物 | |
CN105949424A (zh) | 一种食品包装用tpu薄膜及其制备方法 | |
JP2003517045A (ja) | ポリε−カプロラクトン可塑剤及びそれによって可塑化したビニル系ポリマー組成物 | |
KR100724553B1 (ko) | 가소제 조성물 및 이를 포함하는 폴리염화비닐 수지 조성물 | |
TUKUR et al. | Investigation of structural, thermal and dielectric properties of PVC/modified magnetic nanoparticle composites | |
CN105273284B (zh) | 一种高稳定性橡胶排气助剂及其制造方法 | |
CA2340715C (fr) | Procede de production d'un article sterile |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 07746732 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 07746732 Country of ref document: EP Kind code of ref document: A1 |